Production of hydrocarbons of low boiling point



Patented Apr. 12, 1932 UNITED STATES iPATENT' OFFICE ERNST GALLE,

OF LUDWIGSEAFEIN -ON-'1HE-REINE, AND GEBHiAR-DT HQFMANN All!) EERMANN ZOBN, OF MANNHEIM, GERMANY, ASSIGNORS 130 I. G; FABBENINIDUSTRZIE AKTEENGESELLSGHAET, E ERANKE RT QN-THE-MAIN,

No Drawing. Application filed septcmber 3, rear, Serial Ha. 217,582. and in Germany September $1926- mean metals and alloys which have been renvation' of the metals dered particularly reactive by treatment with solutions of metal salts.

It has been found that in this process especially aluminium, but also numerous other metals, such as copper, lead, magnesium, iron; p

cobalt, chromium and the like and also alloys thereof, have a particularly good efiect in the production of low-boiling products when employed in an activated condition. The actiand alloys is efiected by treating the same with a solution of a salt of such metal which in the electromotive series (see for instance Alexander Smith lntrm duction to Inorganic Chemistry, 3rd edition, page 04) ranges below the metal to be activated and which is solid at room temperature. By this treatment the metal of the salt is precipitated in a state of iinedistribution in the metallic or oxidic form upon the catalytic metal to be activated. This activation proceeds most effectively alloy has been etched beforehand with caustic soda solution, hydrochloric acid or the like, if necessary after washing with alcohol or ether. The catalysts prepared in this manner are excellently adapted for the-conversion of tars and mineral oils, and their distillation products and the like with or without the application of elevated pressure. In some cases, especially favorable yields may be obtained if the activated metals, instead of being used alone, are employ-ed in admixture with anhydrous metal chlorids and in part-icchlorid. The opular anhydrous aluminium eration is preferably conducted while stirring". 1 I The process according to the present invention is applicable to tar oils, also tojtars mineral purified by when the metal or generally such as producer tar, and also to zene and toluene, in addition to other light hydrocarbons, and which are therefore particularly suitable as motor fuels, can be 0b. tamed, according to this process.

By treating for example a crude mineral oiloor in low boiling constituents with activated aluminium and hydrochloric acid gas, at temperatures over 100 (3., approximately 80 per cent of products boiling up to 200 We are obtained.

The valuable hydrocarbons of low boiling point obtained byv this process need not be troublesome and expensive operations, but it is suficient to wash them with dilute caustic soda solution or to subject them to steam distillation. The products GERMilNY, A GOREQEATKQN lld are clear and colorless and do not become colored by the action oii light and air. They are practically completely saturated and consist of parafidn hydrocarbons naphthenes or aromatic hydrocarbons, or in varied propu'tioin: depending on the nacure of the initial materials employed.

We have further found that the yield in valuable saturated aliphatic hydrocarbons of very low boiling; point may be considerably increased; to this end aliphatic or naphthenic hydrocarbons of high boiling point are passed through the reaction chamber at so low a velocity that considerable quantities of hydrocarbons boiling below C. are formed. With this end in View, the rate of ilows should be suitablyaccommodated to the other working conditions having regard for example to the nature of the initial material and contact mass, the temperature and the like; and an example of this mode oi? working illustrating the influence of the rate of mixtures thereof ill) be given hereinafter. With other initial materials and other catalysts etc., the speed must again be adapted to the circumstances of each particular case.

The recovery of the low-boiling cracked products may be effected by strong cooling or compression, or both, orby means of adsorption or absorption agents, preferably in such a manner that fractionation occurs at the same time.

The requisite heat is preferably supplied to the reaction chamber by external heating and by preheating the initial material. The operation may also be carried on in the presence of inert gases, such as hydrogen, or

nitrogen, or vapors. The following examples will further illustrate the nature of the said invention which however is not limited thereto. The parts are by weight.

4 Example 1 Activated aluminium turnings are allowed to act, in the presence of dry hydrochloric Example 2 100 parts of producer tar from brown-coal .are heated to above 150 C. with 10 parts of granular aluminium activated by zinc chlorid, a current of hydrochloric acid gas being passed through while stirring, 70

parts of a liquid product are obtained, of which about 50 per cent up to 200 C.

Example 3 100 parts of a fraction boiling from 200 to 400 C. of a product from the destructive hydrogenation of coal by treatment with hydrogen under pressure are treated t temperatures from 120 to 160 with 'dry ydrochloric acid gas, while stirring and in the presence of aluminium turnings activated by copper chlorid. 77 per cent of a distillate are obtained, of which 78 per cent boils up to Example 4 100 parts of a portion of mineral oil which is soluble in sulfurous acid are heated to from 150 to 220 with 1 part of aluminium turnings activated by uranium nitrate and 1 part of aluminium turnings activated by s11- ver nitrate, while passing through hydrochlorie acid gas. 53 per cent'of a distillate are obtained, 25 per cent of which consists of benzene and toluene.

E xample 5 700 parts of such portions of a mineral oil as are soluble in liquid sulfurous acid, are heated to 170 C., while actively stirring, with 14 parts of anhydrous aluminium chlorid and 14 parts of granular aluminium activated by silver nitrate, dry hydrogen chlorid being passed through. 60 per cent of a distillate boiling below 200 C. are obtained, 32 per cent of which consists of benzene and toluene. 0

Example I The following typical example demonstrates clearly the influence exerted on the character of the products by the rate of flow of theinitial material through the contact chamber. i By passing a mineral oil fraction, boiling between 220 and 285 C. at the rate of 100 cc. per hour through a contact chamber of 500 cc. capacity, charged with sheet aluminium activated by nickel chlorid and heated to 200 C., with the addition of hydrogen chlorid, there is obtained, in an air-cooled receiver, 84 per cent of a condensate, 31 per cent of which boils between and 200 C. in addition to which 10 per cent of condensate is obtained by strongly cooling to the temperature of solid carbon dioxid. On the rate of flow being reduced to one-third, the air cooled receiver contains 50 per cent of condensate', 47 per cent of which boils between 70 and 200 C. whilst strongly cooling furnishes 44 per cent of condensate. On lowering the rate of flow to one-sixth, 96 per cent of condensate .is' obtained in the strongly cooled receiver, whereas air-cooling furnishes no condensate at all. The condensates obtained by cooling to the temperature of solid carbon dioxid, consist of a small amount of ethane, 10 to 20 per cent of propane, 30 to 40 per cent of butane, 30 to 40 per cent of pentane and 5 to 10 per cent of hexane.

What we claim is:

1. The process of producing hydrocarbons of low boiling point which'comprises acting on hydrocarbons of high boiling point with a gaseous halogen hydrid at temperatures above 100 C. in the presenceof an activated metal selected from the group consisting of aluminium, copper, lead, magnesium, iron, cobalt, chromium and alloys thereof, said metal being activated by treatment with a solution of a salt of a metal which is solid at room temperature and which in the electromotive series of the metals rangesbelow the metal to be activated.

2. The process of producing hydrocarbons of low boiling point which comprises acting on hydrocarbons of high boiling point with hydrochloric acid gas at temperatures above 100 C in the presence of aluminium-activated bya treatment with a solution of a salt of a metal which is solid at room temperature and which in the electromotive series ranges below'aluminium.

3. The process of producing hydrocarbons of low boiling point which comprises acting on hydrocarbons of high boiling point with hydrochloric acid gas at temperatures above 100 C. in, the presence of aluminium activated by a treatment with a solution of a salt of a metal, which is solid at room temperature and which in the electromotive series of the metals ranges below aluminum, and aluminium chlorid.

the metal to be activated.-.

5. Theiprocess of producing hydrocarbons of low boiling point which comprises actm on hydrocarbons of high boiling point wit a gaseous halogen hydrid at temperatures between 100 and 220 C. in the presence of a metal of the group of metals which are electropositiveto copper and including copper, activated by a treatment with a solution of a salt of'a metal which is solid at room temperature and which in the elect-romotive series of the metals ranges below the metal to be activated. x

6. The process of producing hydrocarbons of low boiling point which comprises acting on hydrocarbons of high-boiling point wit the group of metals which are electropositive to copper and including copper which is activated y a treatment with a solution of a salt of a metal which is solid at room tempera .ture and which in the electromotive senes of the metals ranges below the metal to be acti vated and an anhydrous metal chlorid.

9. The process of producing hydrocarbons of low boiling point which comprises acting on non-aromatic hydrocarbons of high boilmg point with a gaseous halogen hydrid at temperatures above 100C. in the presence of a metal of the group of metals which are electropositive to copper and including copper which is agtivatedby a treatment with a solution of a salt of a metal which is solid at room temperature and which in the electromotive series ranges below the metal to be activated, the speed of the said non-aromatic hydrocarbons being'chosen so low that considerable quantities of hydrocarbons boiling below 7 C. are formed.- 7

10. The process of producing hydrocarbons 1 of low boiling point which comprises stirring hydrocarbons of high boiling point with a gaseous halogen hydrid at temperatures above 100 C. in the presence of a metal of the group of metals which are electropositive to copper and including copper which is activated y a treatment with a solution of a salt of a metal which is solid at room temperature and which in the electromotive series of the metals ranges below the metals to be activated. In testimony whereof we have hereunto set our hands. 1

I ERNST GALLE.

GERHABDT HOFMANN. HERMANN ZORN.

hydrochloric acid gas at temperatures between 100 and Q C. in the presence of aluminium'activated by a treatment with a solution of asalt of a metal which in the electromotive series ranges below aluminium.

7 .,The recess of producing hydrocarbons of low boiling point which comprises acting on hydrocarbons of hi h boiling point with a gaseous halogen hy rid at temperatures above 100 C. in the resence of a metal of the group of metals w ieh are electropositive y a treatment with a solution of a salt of a-metal which is solid at room temperature and which in the electromotive series of the metals ranges below the metal to be activated.

8: The process of producing hydrocarbons I of low boiling point which comprises acting on hydrocarbons of hi h boiling point'with r and including copper which is actia gaseous halogen hy rid at temperatures above 100 C. in the presence of a metal of 

